Pt Nanoparticles on Mg(OH)₂ for the Selective Hydrogenation of Furfural to Furfuryl Alcohol

Manipulating the Electronic Metal–Support Interaction (EMSI) in metal catalysts supported on various substrates has proven to be the most efficient strategy for adjusting the electronic structure and enhancing the catalytic efficiency. However, a comprehensive understanding of the electronic charge transfer mechanism during the catalytic process has been challenging to grasp. Herein, Pt-PtO x /Mg(OH) 2 -F (where F denotes a flower-like structure) was synthesized through a combination of the gas–liquid interface method and the sol–gel method. The catalyst features a uniform three-dimensional flower-like morphology assembled from ultrathin nanosheets, forming a nanostructured architecture with high surface area and abundant exposed active sites, which significantly enhances mass transport and catalytic accessibility. This nanostructured catalyst enabled the efficient conversion of furfural (FF), a biomass platform compound, into furfuryl alcohol (FA), achieving a furfural conversion of 99.9% and a furfuryl alcohol selectivity of 98.4%, with a turnover frequency (TOF) value of 333.96 h –1, which is higher than the performance of most catalysts. Evidence from EXAFS, XPS, CO pulse spectroscopy, and theoretical calculations indicated electronic disruptions between Pt species and the Mg(OH) 2 support, wherein charge redistribution has a direct impact on the adsorption behavior during the catalytic procedure. The Pt–O bonds formed through orbital hybridization altered the charge state of surface Pt sites, directing more electrons toward the furfural intermediate (C 4 H 3 O–CHO*), thereby facilitating adsorption. Ultimately, the active sites of the Pt-PtO x /Mg(OH) 2 -F catalyst were composed of Pt δ+ Lewis acid sites and OH δ− Lewis base sites, with the furfural carbonyl coordinating with the oxygen atoms of ethanol and Pt δ+ sites, forming a six-membered ring transition state that eventually achieved the reduction of the furfural carbonyl.